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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2025

Action at a distance: The remarkable coupling of CO 2 uptake to electron transfer in specialized cyanobacterial NDH-1 complexes

Cyanobacteria achieve highly efficient photosynthesis using a CO 2 -concentrating mechanism relying on specialized Type I (NDH-1) complexes. Among these, NDH-1 3 and NDH-1 4 catalyze redox-coupled hydration of CO 2 to bicarbonate, supporting carbon fixation in carboxysomes. The mechanism of coupling electron transfer to CO 2 -hydration by these variant NDH-1 complexes remains unknown. We engineered a Synechococcus PCC7942 strain that expresses exclusively the high flux/low affinity NDH-14 complex, enabling the observation of the coupling of CO 2 hydration to cyclic electron flow in isolation from the other NDH-1 isoforms normally present in cells. We found that inhibition of the CupB protein by the carbonic anhydrase inhibitor ethoxzolamide (EZ) suppressed CO 2 uptake, slowed photosystem I rereduction, and abolished proton pumping as probed by acridine orange fluorescence. These effects were absent in strains lacking Cup proteins, confirming specificity. The results demonstrate that CO 2 hydration and electron transfer through NDH-14 are tightly coupled via proton translocation across the thylakoid membrane. These findings provide direct evidence for the bidirectional interaction in bioenergetic coupling between the plastoquinone reduction and the CO 2 uptake at the distal Zn-site over a span of ~150 Å and support a proton-removal hypothesis involving the proton transfer pathways from the Zn-site of CO2 hydration to an energetically coupled proton loading site evolutionarily repurposed from the ancestral proton pumping mechanism to enable energetic CO 2 uptake.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Measuring Thickness-Dependent Relative Light Yield and Detection Efficiency of Scintillator Screens

Digital camera-based neutron imaging systems consisting of a neutron scintillator screen optically coupled to a digital camera are the most common digital neutron imaging system used in the neutron imaging community and are available at any state-of-the-art imaging facility world-wide. Neutron scintillator screens are the integral component of these imaging system that directly interacts with the neutron beam and dictates the neutron capture efficiency and image quality limitations of the imaging system. This work describes a novel approach for testing neutron scintillators that provides a simple and efficient way to measure relative light yield and detection efficiency over a range of scintillator thicknesses using a single scintillator screen and only a few radiographs. Additionally, two methods for correlating the screen thickness to the measured data were implemented and compared. An example 6LiF:ZnS scintillator screen with nominal thicknesses ranging from 0–300 μm was used to demonstrate this approach. The multi-thickness screen and image and data processing methods are not exclusive to neutron scintillator screens but could be applied to X-ray imaging as well. This approach has the potential to benefit the entire radiographic imaging community by offering an efficient path forward for manufacturers to develop higher-performance scintillators and for imaging facilities and service providers to determine the optimal screen parameters for their particular beam and imaging system.

42 ENGINEERING↗
DOE OSTI2017

Assessing plant community composition fails to capture impacts of white-tailed deer on native and invasive plant species

Excessive herbivory can have transformative effects on forest understory vegetation, converting diverse communities into depauperate ones, often with increased abundance of non-native plants. White-tailed deer are a problematic herbivore throughout much of eastern North America and alter forest understory community structure. Reducing (by culling) or eliminating (by fencing) deer herbivory is expected to return understory vegetation to a previously diverse condition. We examined this assumption from 1992 to 2006 at Fermilab (Batavia, IL) where a cull reduced white-tailed deer ( Odocoileus virginianus ) abundance in 1998/1999 by 90 % from 24.6 to 2.5/km 2 , and at West Point, NY, where we assessed interactive effects of deer, earthworms, and invasive plants using 30 × 30 m paired fenced and open plots in 12 different forests from 2009 to 2012. We recorded not only plant community responses (species presence and cover) within 1 m 2 quadrats, but also responses of select individual species (growth, reproduction). At Fermilab, introduced Alliaria petiolata abundance initially increased as deer density increased, but then declined after deer reduction. The understory community responded to the deer cull by increased cover, species richness and height, and community composition changed but was dominated by early successional native forbs. At West Point plant community composition was affected by introduced earthworm density but not deer exclusion. Native plant cover increased and non-native plant cover decreased in fenced plots, thus keeping overall plant cover similar. At both sites native forb cover increased in response to deer reduction, but the anticipated response of understory vegetation failed to materialize at the community level. Deer-favoured forbs ( Eurybia divaricata, Maianthemum racemosum, Polygonatum pubescens and Trillium recurvatum ) grew taller and flowering probability increased in the absence of deer. Plant community monitoring fails to capture initial and subtle effects of reduced or even cessation of deer browse on browse sensitive species. As a result, measuring responses of individual plants (growth, flowering and reproductive success) provides a more sensitive and powerful assessment of forest understory responses to deer management.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Results from a search for dark matter in the complete LUX exposure

Here, we report constraints on spin-independent weakly interacting massive particle (WIMP)-nucleon scattering using a 3.35 ×10 4 kg day exposure of the Large Underground Xenon (LUX) experiment. A dual-phase xenon time projection chamber with 250 kg of active mass is operated at the Sanford Underground Research Facility under Lead, South Dakota (USA). With roughly fourfold improvement in sensitivity for high WIMP masses relative to our previous results, this search yields no evidence of WIMP nuclear recoils. At a WIMP mass of 50 GeV c –2 , WIMP-nucleon spin-independent cross sections above 2.2 ×10 –46 cm 2 are excluded at the 90% confidence level. When combined with the previously reported LUX exposure, this exclusion strengthens to 1.1 × 10 –46 cm 2 at 50 GeV c –2 .

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

New Concepts in Electrolytes

Over the past decades, Li-ion battery (LIB) has turned into one of the most important advances in the history of technology due to its extensive and in-depth impact on our life. Its omnipresence in all electric vehicles, consumer electronics and electric grids relies on the precisely tuned electrochemical dynamics and interactions among the electrolytes and the diversified anode and cathode chemistries therein. Furthermore, with consumers' demand for battery performance ever increasing, more and more stringent requirements are being imposed upon the established equilibria among these LIB components, and it became clear that the state-of-the-art electrolyte systems could no longer sustain the desired technological trajectory. Driven by such gap, researchers started to explore more unconventional electrolyte systems. From superconcentrated solvent-in-salt electrolytes to solid-state electrolytes, the current research realm of novel electrolyte systems has grown to unprecedented levels. In this review, we will avoid discussions on current state-of-the-art electrolytes but instead focus exclusively on unconventional electrolyte systems that represent new concepts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Study of charm hadronization with prompt $ {\Lambda}_{\textrm{c}}^{+} $ baryons in proton-proton and lead-lead collisions at $ \sqrt{s_{\textrm{NN}}} $ = 5.02 TeV

The production of prompt $ {\Lambda}_{\textrm{c}}^{+} $ baryons is measured via the exclusive decay channel $ {\Lambda}_{\textrm{c}}^{+}\to p{\textrm{K}}^{-}{\pi}^{+} $ at a center-of-mass energy per nucleon pair of 5.02 TeV, using proton-proton (pp) and lead-lead (PbPb) collision data collected by the CMS experiment at the CERN LHC. The pp and PbPb data were obtained in 2017 and 2018 with integrated luminosities of 252 and 0.607 nb$^{−1}$, respectively. The measurements are performed within the $ {\Lambda}_{\textrm{c}}^{+} $ rapidity interval |y| < 1 with transverse momentum (p$_{T}$) ranges of 3–30 and 6–40 GeV/c for pp and PbPb collisions, respectively. Compared to the yields in pp collisions scaled by the expected number of nucleon-nucleon interactions, the observed yields of $ {\Lambda}_{\textrm{c}}^{+} $ with p$_{T}$> 10 GeV/c are strongly suppressed in PbPb collisions. The level of suppression depends significantly on the collision centrality. The $ {\Lambda}_{\textrm{c}}^{+} $/D$^{0}$ production ratio is similar in PbPb and pp collisions at p$_{T}$> 10 GeV/c, suggesting that the coalescence process does not play a dominant role in prompt $ {\Lambda}_{\textrm{c}}^{+} $ baryon production at higher p$_{T}$.[graphic not available: see fulltext]

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

Probing Nitrogen-Doping Effects in the Core-Shell Structured Catalysts for Bifunctional Electrocatalysis.

The design of core-shell structured catalysts has attracted wide interests due to their remarkable catalytic performances in many fields. Although the nitrogen doping is often integrated in such kind of catalysts, the main contribution is exclusively attributed to the metal sites or the core-shell configuration. The role of nitrogen doping is often believed to be less important, which remains largely unexplored. Here, in an effort to probe the catalytic role of heterogeneous doping in such core-shell structure, the effect of nitrogen doping on the activation of cobalt and iron carbide-based materials for the electrocatalytic reduction of oxygen and the hydrogen evolution reaction is originally revealed. The nitrogen doping in the core-shell structured biphasic interfaces is found to be of critical importance for triggering the electrocatalytic activity and selectivity. Therefore, this study shows the neglected but critical role of nitrogen doping and biphasic interactions in a core-shell configuration, paving a new pathway towards the performance enhancement.

biphasic interfaces↗
DOE OSTI2019

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

In the framework of density functional theory (DFT), the lowest triplet excited state (T1) can be evaluated using multiple formulations, the most straightforward of which are unrestricted density functional theory (UDFT) and time-dependent density functional theory (TDDFT). Assuming the exact exchange-correlation (XC) functional is applied, UDFT and TDDFT provide identical energies for T1 ( ET), which is also a constraint that we require our XC functionals to obey. However, this condition is not satisfied by most of the popular XC functionals, leading to inaccurate predictions of low-lying, spectroscopically and photochemically important excited states, such as T1 and the lowest singlet excited state (S1). Inspired by the optimal tuning strategy for frontier orbital energies [T. Stein, L. Kronik, and R. Baer, J. Am. Chem. Soc. 2009, 131, 2818], we proposed a novel and nonempirical prescription of constructing an XC functional in which the agreement between UDFT and TDDFT in ET is strictly enforced. Referred to as "triplet tuning", our procedure allows us to formulate the XC functional on a case-by-case basis, using the molecular structure as the exclusive input, without fitting to any experimental data. The first triplet tuned XC functional, TT-ωPBEh, is formulated as a long-range-corrected (LRC) hybrid of Perdew-Burke-Ernzerhof (PBE) and Hartree-Fock (HF) functionals [M. A. Rohrdanz, K. M. Martins, and J. M. Herbert, J. Chem. Phys. 2009, 130, 054112] and tested on four sets of large organic molecules. Compared to existing functionals, TT-ωPBEh manages to provide more accurate predictions for key spectroscopic and photochemical observables, including but not limited to ET, the optical band gap ( ES), the singlet-triplet gap (Δ EST), and the vertical ionization potential ( I⊥), as it adjusts the effective electron-hole interactions to arrive at the correct excitation energies. This promising triplet tuning scheme can be applied to a broad range of systems that were notorious in DFT for being extremely challenging.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Biogenic sulfide control by nitrate and (per)chlorate – A monitoring and modeling investigation

Biosouring is commonly encountered during secondary oil recovery when seawater or another high sulfate water source is utilized for flooding; as a result, effective souring control is of great interest to the oil industry. Here we describe a laboratory study to evaluate the relative effectiveness of souring interventions through the injection of nitrate, chlorate and perchlorate, collectively (per)chlorate, solutions and whether in-situ galvanic potential measurements can be used for convenient and quantitative tracking of sulfide dynamics. Nitrate has typically been the chemical of choice for souring treatments, while the efficacy of (per)chlorate as a new candidate inhibitor has only been explored recently. (Per)chlorate is known to inhibit oil reservoir souring via mechanisms such as toxicity, bio-competitive exclusion and sulfur redox cycling. Two sets of experiments under different matrix and inoculation conditions were conducted to evaluate treatment efficiency under variable baseline physical and biogeochemical conditions. Our data demonstrated the sensitivity of the galvanic potential signals to sulfide concentrations where the sulfide-galvanic potential correlation is similar to the theoretical predictions based on the Nernst equation, demonstrating the feasibility of using galvanic potential as a quick and economical method for quantifying in situ sulfide concentrations for tracking reservoir souring processes and subsequent intervention effectiveness. Our results show that all three chemicals were effective at suppressing sulfidogenesis. A reactive transport model for perchlorate treatment was developed to simulate the reaction processes and explore the interactions between the underlying competing mechanisms of this inhibitor. A baseline simulation captured the temporal patterns of the effluent chemical species. Subsequent simulations in which individual inhibition mechanisms were systematically removed elucidated the relative role that each inhibition mechanism played at the different phases of the experiment. The simulation results complement the experimental findings. Our study supports the potential advantages of souring control with (per)chlorate treatments, and the application of galvanic signal as an economic, in-situ monitoring approach for tracking souring dynamics and treatment efficacy.

02 PETROLEUM↗
DOE OSTI2021

Strategies for microgrid operation under real-world conditions

Microgrids are an increasingly relevant technology for integrating renewable energy sources into electricity systems. Based on a microgrid implementation in California, in this study we investigate microgrid operation under real-world conditions. These conditions have not yet been considered in combination and encompass energy charges, demand charges, export limits, as well as uncertainty about future electricity demand and generation in the microgrid. Under these conditions, we evaluate the performance of two frequently applied groups of strategies for microgrid operation. The first group is composed of proactive strategies that optimize decisions based on forecasts of future electricity generation and demand. The second group includes reactive strategies that make operational decisions based exclusively on the current state of the microgrid. We evaluate the performance of the strategies under varying operational parameters, forecast accuracies, and microgrid configurations—well beyond our Californian showcase. Our results confirm the expectation that proactive strategies outperform reactive ones in the majority of settings. Yet, reactive strategies can perform better under short control intervals or under moderate prediction errors of PV generation or demand. Furthermore, the interplay between real-world conditions and operational strategies reveals several additional insights for research on microgrid operation. First, we find that demand charges and export limits decisively affect microgrid performance. Second, the impact of forecast errors is highly non-linear and non-monotonous. Third, escalating negative interactions between forecast errors and demand charges make proactive strategies benefit from longer control intervals. This result is contrary to existing best practice, which promotes short control intervals to minimize the impact of uncertainty.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2023

Synthesis and morphological characterization of linear and miktoarm star poly(solketal methacrylate)- block -polystyrene copolymers

The synthesis, molecular characterization, and morphological evaluation of AB n, (n = 2,3) miktoarm star block copolymers consisting of poly(glycerol monomethacrylate) (PGMA) and polystyrene (PS) with varying molecular weights and compositions is described. The system is known to demonstrate a remarkably high Flory-Huggins interaction parameter. The corresponding linear diblock copolymer analogues, were synthesized as well, and comparisons with regard to feature dimensions and morphologies are provided. Well-ordered nanostructures of various morphologies were formed with domain spacing as low as 7.2 nm. Different morphologies were attained by some of the topological isomers indicating that in miktoarm star block copolymers the phase boundaries were strongly shifted. Additionally, a triblock ABA analogue was studied to investigate the effect of triblock copolymer conformations. Noteworthy is that for copolymers with different macromolecular architecture leading to similar morphology; different domain spacings were obtained. The synthesis of all the samples was carried out by high-vacuum anionic polymerization techniques. Molecular characterization with Size Exclusion Chromatography (SEC) and Proton Nuclear Magnetic Resonance Spectroscopy ( 1 H NMR) confirmed well-defined copolymers obtained. The morphological characterization was accomplished by Small-Angle X-ray Scattering (SAXS). In conclusion, the observations from this study highlight the potential of incorporating macromolecular architecture in the self-assembly of strongly immiscible block copolymers to attain ultra-small nanofeatures with desired morphologies.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Production of Λ c + baryons in proton-proton and lead-lead collisions at s NN = 5.02 TeV

The transverse momentum ( p T ) spectra of inclusively produced Λ c + baryons are measured via the exclusive decay channel Λ c + → p K – π + using the CMS detector at the LHC. Spectra are measured as a function of transverse momentum in proton-proton ( p p ) and lead-lead (PbPb) collisions at a nucleon-nucleon center-of-mass energy of 5.02 TeV. The measurement is performed within the Λ c + rapidity interval | y | < 1 in the p T range of 5–20 GeV/ c in p p and 10–20 GeV/ c in PbPb collisions. The observed yields of Λ c + for p T of 10–20 GeV/ c suggest a suppression in central PbPb collisions compared to p p collisions scaled by the number of nucleon-nucleon (NN) interactions. The Λ c + / D 0 production ratio in p p collisions is compared to theoretical models. In PbPb collisions, this ratio is consistent with the result from p p collisions in their common p T range.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Structural insight into host plasma membrane association and assembly of HIV-1 matrix protein

Oligomerization of Pr55 Gag is a critical step of the late stage of the HIV life cycle. It has been known that the binding of IP6, an abundant endogenous cyclitol molecule at the MA domain, has been linked to the oligomerization of Pr55 Gag . However, the exact binding site of IP6 on MA remains unknown and the structural details of this interaction are missing. Here, we present three high-resolution crystal structures of the MA domain in complex with IP6 molecules to reveal its binding mode. Additionally, extensive Differential Scanning Fluorimetry analysis combined with cryo- and ambient-temperature X-ray crystallography and GNM-based transfer entropy calculations identify the key residues that participate in IP6 binding. Our data provide novel insights about the multilayered HIV-1 virion assembly process that involves the interplay of IP6 with PIP2, a phosphoinositide essential for the binding of Pr55 Gag to membrane. IP6 and PIP2 have neighboring alternate binding sites within the same highly basic region (residues 18–33). This indicates that IP6 and PIP2 bindings are not mutually exclusive and may play a key role in coordinating virion particles’ membrane localization. Based on our three different IP6-MA complex crystal structures, we propose a new model that involves IP6 coordination of the oligomerization of outer MA and inner CA domain’s 2D layers during assembly and budding.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Nonresonant central exclusive production of charged-hadron pairs in proton-proton collisions at s = 13 TeV

The central exclusive production of charged-hadron pairs in p p collisions at a center-of-mass energy of 13 TeV is examined, based on data collected in a special high- β * run of the LHC. The nonresonant continuum processes are studied with the invariant mass of the centrally produced two-pion system in the resonance-free region, m π + π − < 0.7 or m π + π − > 1.8 GeV . Differential cross sections as functions of the azimuthal angle between the surviving protons, squared exchanged four-momenta, and m π + π − are measured in a wide region of scattered proton transverse momenta, between 0.2 and 0.8 GeV, and for pion rapidities | y | < 2 . A rich structure of interactions related to double-pomeron exchange is observed. A parabolic minimum in the distribution of the two-proton azimuthal angle is observed for the first time. It can be interpreted as an effect of additional pomeron exchanges between the protons from the interference between the bare and the rescattered amplitudes. After model tuning, various physical quantities are determined that are related to the pomeron cross section, proton-pomeron and meson-pomeron form factors, pomeron trajectory and intercept, and coefficients of diffractive eigenstates of the proton. © 2024 CERN, for the CMS and TOTEMs Collaboration 2024 CERN

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2017

Spatial complexity of carcass location influences vertebrate scavenger efficiency and species composition

Scavenging plays an important role in shaping communities through inter- and intra-specific interactions. Although vertebrate scavenger efficiency and species composition is likely influenced by the spatial complexity of environments, heterogeneity in carrion distribution has largely been disregarded in scavenging studies. We tested this hypothesis by experimentally placing juvenile bird carcasses on the ground and in nests in trees to simulate scenarios of nestling bird carrion availability. We used cameras to record scavengers removing carcasses and elapsed time to removal. Carrion placed on the ground was scavenged by a greater diversity of vertebrates and at > 2 times the rate of arboreal carcasses, suggesting arboreal carrion may represent an important resource to invertebrate scavengers, particularly in landscapes with efficient vertebrate scavenging communities. Nonetheless, six vertebrate species scavenged arboreal carcasses. Rat snakes (Elaphe obsolete), which exclusively scavenged from trees, and turkey vultures (Cathartes aura) were the primary scavengers of arboreal carrion, suggesting such resources are potentially an important pathway of nutrient acquisition for some volant and scansorial vertebrates. Our results highlight the intricacy of carrion-derived food web linkages, and how consideration of spatial complexity in carcass distribution (i.e., arboreal) may reveal important pathways of nutrient acquisition by invertebrate and vertebrate scavenging guilds.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Investigation of the background in coherent J/ψ production at the EIC

Understanding various fundamental properties of nucleons and nuclei is among the most important scientific goals at the upcoming Electron-Ion Collider (EIC). With the unprecedented opportunity provided by the next-generation machine, the EIC might provide definitive answers to many standing puzzles and open questions in modern nuclear physics. We investigate one of the golden measurements proposed at the EIC, which is to obtain the spatial gluon density distribution within a lead (Pb) nucleus. The proposed experimental process is the exclusive J/ψ vector-meson production off the Pb nucleus: e + Pb → e' + J/ψ + Pb'. The Fourier transformation of the momentum transfer |t| distribution of the coherent diffraction is the transverse gluon spatial distribution. In order to measure it, the experiment has to overcome an overwhelmingly large background arising from the incoherent diffractive production, where the nucleus Pb' mostly breaks up into fragments of particles in the far-forward direction close to the hadron-going beam rapidity. We systematically study the rejection of incoherent J/ψ production by vetoing products from these nuclear breakups—protons, neutrons, and photons—which is based on the BeAGLE event generator and the most up-to-date EIC Far-forward Interaction Region design. The achieved vetoing efficiency, the ratio between the numbers of vetoed events and total incoherent events, ranges from about 80% to 99% depending on |t|. Assuming a 5% smearing applied to the reconstructed |t| resolution in the Sar t re model, this vetoing efficiency can suppress the incoherent background to at least the first minimum of the coherent |t| distribution. Experimental and accelerator machine challenges as well as potential improvements are discussed herein.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2019

Additively manufacturable micro-mechanical logic gates

Early examples of computers were almost exclusively based on mechanical devices. Although electronic computers became dominant in the past 60 years, recent advancements in three-dimensional micro-additive manufacturing technology provide new fabrication techniques for complex microstructures which have rekindled research interest in mechanical computations. Here we propose a new digital mechanical computation approach based on additively-manufacturable micro-mechanical logic gates. The proposed mechanical logic gates (i.e., NOT, AND, OR, NAND, and NOR gates) utilize multi-stable micro-flexures that buckle to perform Boolean computations based purely on mechanical forces and displacements with no electronic components. A key benefit of the proposed approach is that such systems can be additively fabricated as embedded parts of microarchitected metamaterials that are capable of interacting mechanically with their surrounding environment while processing and storing digital data internally without requiring electric power.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Layer-by-layer deposition of ultra-thin hybrid/microporous membrane for CO 2 separation

Based on two issued US patent, US7947579B2 and US8187678B2 that were invented by our team member at the University of New Mexico and Sandia National Labs, using atomic layer deposition technique (ALD) and molecular self-assembly or templating technique, An ultra-thin CO 2 membrane with CO 2 permeance up to 1580 GPU and CO 2 /N 2 up to 62 has been achieved in phase I project, promising for cost-effective CO 2 separations. As the first step of the project, a robust membrane fabrication protocol was established. To address the defects in the membrane structure, ALD treatment on AO support, multiple dip-coating processes and slow calcination steps were adopted. Consequently, defects were no longer evident in the nanoporous support, which ensures a reliable procedure for lab-scale membrane fabrications as well as the high-fidelity experimental findings. The same procedures may also be helpful for future scaling-up protocols. The layer-by-layer membrane fabrication was started by using a bridged disilane BTEE as the ALD precursor, wherein the organic groups at the bridging site were expected to be aligned layer-by-layer to form Angstrom-channels for CO 2 transport. Using 2-level factorial experimental design, we have found that ALD reaction time and ALD temperature were important factors impacting the CO 2 permeance and selectivity. Longer reaction time and higher ALD temperature were found to be advantageous for better CO 2 permeance and selectivity, which is in agreement with our model that better-aligned CO 2 -channels formed by the layer-by-layer stacking of the organic ligands can be achieved by a slower “stacking” process (longer reaction time) and stronger self-alignment tendency (higher ALD temperature). This observation will be an important guidance for our future membrane designs. The CO 2 -channel templated by –(CH 2 ) 2 - in BTEE was found to be too tight to facilitate fast CO 2 transport, but larger channel diameter is in contradiction with higher CO 2 selectivity. Therefore, the size-exclusion mechanism by itself is not sufficient for effective CO 2 separation. For this reason, the chemistry of the CO 2 -channel has to be carefully tuned. An amine bridged-disilane BTMA was therefore used as ALD precursor for larger CO 2 channel and high CO 2 -affinity chemistry. For BMTA membrane with amine chemistry measured at 100C, the CO 2 permeance was 1030 GPU for 100-cycle-ALD sample with CO 2 /N 2 selectivity of 17, and 302 GPU for 200-cycle-ALD sample with CO 2 /N 2 selectivity of 44. The increase of CO 2 permeance and the CO 2 /N 2 selectivity at elevated temperature is an evidence showing that there is a preferential chemical interaction between CO 2 and –NH functional groups in the membrane, which facilitates selective transport of CO 2 through the membrane. Therefore, using larger organic ligands as the CO 2 -channel template and the introduction of –NH chemistry to the membrane structure were proved to be an effective strategy in achieving better CO 2 permeance and selectivity. Guided by the same strategy, BTMA membrane was irradiated with UV to remove the bridging ligands for larger CO-channel, followed by Zn 2+ and Ni 2+ chemistry modification. Results showed that Zn 2+ or Ni 2+ chemistries will both enhance the selective CO 2 transport thereby the CO 2 /N 2 selectivity, and increasing separation temperature will further improve the CO2 permeance and selectivity. For BTMA membrane with Ni 2+ chemistry measured at 100C, CO 2 permeance of 1580 GPU and CO 2 /N 2 of 62 were achieved, promising for scaled-up industrial applications. Further, same membrane was tested at simulated flue gas condition (with SO 2 at 60C), the CO 2 permeance was 920 GPU and the CO 2 /N 2 selectivity was 52, suggesting the membrane still worked well under simulated flue gas conditions, primarily due to the stable ceramic framework of this membrane.

36 MATERIALS SCIENCE↗